0-diphenols

Epoxy Resins. The chemistry of epoxy resin adhesives is quite varied. However, the most widely used is that formed from the reaction of 4,4 -isopropyhdene diphenol (bisphenol A) [80-05-7] and epichlorohydrin [106-89-8] C H CIO. This epoxy resin is more commonly known as... 

Bisa.codyl, 4,4 -(2-PyridyLmethylene)bisphenol diacetate [603-50-9] (Dulcolax) (9) is a white to off-white crystalline powder ia which particles of 50 p.m dia predominate. It is very soluble ia water, freely soluble ia chloroform and alcohol, soluble ia methanol and ben2ene, and slightly soluble ia diethyl ether. Bisacodyl may be prepared from 2-pyridine-carboxaldehyde by condensation with phenol and the aid of a dehydrant such as sulfuric acid. The resulting 4,4 -(pyridyLmethylene)diphenol is esterified by treatment with acetic anhydride and anhydrous sodium acetate. Crystallisation is from ethanol. 

Thermotropic polycarbonates have been prepared from mixtures of 4,4 -dihydroxybiphenyl and various diphenols (10). Nematic melts were found for copolycarbonates prepared from methyfliydroquiaone, chlorohydroquiaone, 4,4 -dihydroxydiphenyl ether, and 4,4 -dihydroxybenzophenone. Slightly crystalline polycarbonates have been prepared from mixtures of hydroquinone and BPA (T = 154°C, =313°C, AH = 11.0 J/g (2.63 cal/g)), and... 

Liquid crystal polyesters are made by a different route. Because they are phenoHc esters, they cannot be made by direct ester exchange between a diphenol and a lower dialkyl ester due to unfavorable reactivities. The usual method is the so-called reverse ester exchange or acidolysis reaction (96) where the phenoHc hydroxyl groups are acylated with a lower aHphatic acid anhydride, eg, acetic or propionic anhydride, and the acetate or propionate ester is heated with an aromatic dicarboxyHc acid, sometimes in the presence of a catalyst. The phenoHc polyester forms readily as the volatile lower acid distills from the reaction mixture. Many Hquid crystal polymers are derived formally from hydroxyacids (97,98) and thein acetates readily undergo self-condensation in the melt, stoichiometric balance being automatically obtained. 

PPO from tea reacts effectively with both 3 -4 and 3 -4 -5-hydroxylated catechins, with specificity for the o-diphenol (43,44). Studies defining the kinetics of PPO from tea in relation to substrate type are lacking as of this writing (ca 1997). Tea PPO has good functionaUty in the pH range 4.6—5.6 (43,45-48). 

Available Grades. Rhovanil Extra Pure is the trade name of the food-grade vanillin of Rhc ne-Poulenc, worldwide leader in the diphenols area. The following grades are commercially available Rhovanil Extra Pure crystallized, Rhovanil Pine Mesh, Rhovanil Pree Plow, and Rhovanil Liquid. 

There are numerous stmctures that are similar to 2eofites, such as aluminophosphate molecular sieves, AlPOs, but these have not found catalytic apphcations. Zeofites can be modified by incorporation of cations in the crystalline lattice which are not exchangeable ions, but can play catalytic roles. For example, sificahte, which has the stmcture of ZSM-5 but without Al, incorpora ting Ti in the lattice is a commercial catalyst for oxidation of phenol with H2O2 to give diphenols the catalytic sites may be isolated Ti cations (85). 

Polycarbonates. Polyarjiates are aromatic polyesters commonly prepared from aromatic dicarboxylic acids and diphenols. One of the most important polyarylates is polycarbonate, a polyester of carbonic acid. Polycarbonate composite is extensively used in the automotive industry because the resin is a tough, corrosion-resistant material. Polycarbonates (qv) can be prepared from aUphatic or aromatic materials by two routes reaction of a dihydroxy compound with phosgene accompanied by Hberation ofHCl(eq. 5) ... 

Coumarin can also be formed by the reaction of phenol with diketene (40). Similarly, diphenols can react with hydroxycarboxyUc acids or beta-ketoesters to give hydroxycoumaria derivatives. The reaction of resorciaol with malic acid produces umbeUiferone (7-hydroxycoumaria) and its reaction with ethyl acetoacetate gives beta-methylumbeUiferone (7-hydroxy-4-methylcoumaria). 

Hydroxycoumarias can be obtained by reaction of methyl acrylate [96-33-3] with diphenols ia the preseace of aluminum chloride followed by dehydrogeaatioa with palladium oa carboa (43). 

The chemistry of this cure system has been the subject of several studies (44—47). It is now generally accepted that the cure mechanism involves dehydrofluorination adjacent to hexafluoropropylene monomer units. The subsequent fluoroolefin is highly reactive toward nucleophilic attack by a variety of curatives (eg, diamines, diphenols). 

Acid chlorides are useful reagents, but when the pyrazole is N- unsubstituted a dimerization occurs and the diketopiperazine (254) is isolated (Section 4.04.2.3.3(x)). However, (254) reacts with many compounds as an acid chloride would, for example with amines to yield amides (67HC(22)l). The difunctional pyrazole derivative (441) affords polymers by reaction with diphenols (69RRC763). Cyanopyrazoles can be hydrolyzed to the corresponding carboxylic acids (68CB829). 

Dienestrol [4,4 -(diethylidene-ethylene)diphenol, Dienol] [84-17-3] M 266.3, m 227-228, 231-233, pKesi 9.8. Crystd from EtOH or dilute EtOH, sublimes at 130°/lmm. The diacetate has m 119-120 (from EtOH) [Hobday and Short J Chem Soc 609 1943]. 

Saccharin and the three diphenols, pyrocatechol, resorcinol and hydroquinone, react only weakly or not at all. The same is true of picric acid. On the other hand, cyclohexanesulfamic acid and bis-(2-ethylhexyl)-phosphoric acid are readily detected [1]. 

Guaiacol is the monomethyl ether of the diphenol, catechol, or ortho-dihydroxybenzene. Its constitution is—... 

Diphenol/thiophenol is one of the most important polymer precursors for synthesis of poly(aryl ethers) or poly-(aryl sulfides) in displacement polymerizations. Commonly used bisphenols are 4,4 -isopropylidene diphenol or bisphenol-A (BPA) due to their low price and easy availability. Other commercial bisphenols have also been reported [7,24,25]. Recently, synthesis of poly(aryl ethers) by the reaction of new bisphenol monomers with activated aromatic dihalides has been reported. The structures of the polymer precursors are described in Table 2. Poly(aryl ether phenylquinoxalines) have been synthesized by Connell et al. [26], by the reaction of bisphenols containing a preformed quinoxaline ring with... 

Later, Kricheldorf and coworkers [93,94] extensively demonstrated the use of 0-silylated bifunctional monomers, such as diphenols, for synthesis of a wide variety of polycondensation polymers. The silylated oxygen of difunctional phenols may be condensed with activated... 

It is observed that the synthesis of various polymers by the silylated method is superior to the conventional diamine, diphenol, or dithiol route particularly with respect to higher inherent viscosity or molecular weight of the resulting polymers. 

Diphenol carbonate is produced by the reaction of phosgene and phenol. A new approach to diphenol carbonate and non-phosgene route is by the reaction of CO and methyl nitrite using Pd/alumina. Dimethyl carbonate is formed which is further reacted with phenol in presence of tetraphenox titanium catalyst. Decarbonylation in the liquid phase yields diphenyl carbonate. 

Epoxy resins are produced by reacting epichlorohydrin and a diphenol. Bisphenol A is the diphenol generally used. The reaction, a ring... 

Polycarbonates are like polyesters, but their carbonyl group is linked to two -OR groups, [0 C(0R>2l- Lexan, for instance, is a polycarbonate prepared from diphenyl carbonate and a diphenol called bisphenol A. Lexan has an unusually high impact strength, making it valuable for use in machinery housings, telephones, bicycle safety helmets, and bulletproof glass. 

Phenolic compounds are weaker nucleophiles and better leaving groups than aliphatic alcohols. They do not yield polyesters when reacted with carboxylic acids or alkyl carboxy lates. The synthesis of polyesters from diphenols is, therefore, generally carried out through the high-temperature carboxylic acid-aryl acetate or phenyl ester-phenol interchange reactions with efficient removal of reaction by-product (Schemes 2.10 and 2.11, respectively). 

Solution reactions between diacid chlorides and diols or diphenols are carried out in THF or CH2C12 at —10 to 30°C in die presence of tertiary amines such as triethylamine or pyridine, which play a role of both reaction catalyst and HC1 acceptor (Scheme 2.26). This synthetic mediod is also termed acceptor-catalytic polyesterification.295-297 High-temperature solution reactions have also been reported for a number of less soluble, generally semicrystalline, aromatic polyesters.6 They yield high-molar-mass polyesters exhibiting good mechanical properties and thermal stability. 

Activating agents, such as trifluoroacetic anhydride 1,1 -carbonyldiimidazolc carbodiimides sulfonyl, tosyl, and picryl chlorides and a range of phosphorus derivatives can promote direct solution reactions between dicarboxylic acids and diols or diphenols in mild conditions. The activating agents are consumed during the reaction and, therefore, do not act as catalysts. These so-called direct polycondensation or activation polycondensation reactions proceed via the in situ transformation of one of the reactants, generally the carboxylic acid, into a more... 

Trinitrochlorobenzene (piciyl chloride) in pyridine-A -mcthylpyrrolidi-none (NMP) solutions were later used for the preparation of polyesters from dicarboxylic acids and diphenols or aliphatic diols,309 but better results have been obtained with sulfonyl chlorides and phosphorus compounds. 

However, many salts such as the hydroquinone or biphenol salt are so insoluble diat they do not work well by this procedure. Furthermore, a stoichiometric amount of base used for die reaction is critical to obtain high-molecular-weight polymers. Moreover, die sd ong base may undesirably hydrolyze the dihalides to afford deactivated diphenolates, which upset the stoichiometry. Clendining et al. reported that potassium carbonate or bicarbonate could be used in these reactions instead of corresponding hydroxides.60 McGrath and co-workers were the first to systematically study die use of the weak base K2C03 instead of a strong base to obtain phenolate salts.8,61,62 Potassium carbonate was found to be better than... 

The nucleophilic aromatic substitution reaction for the synthesis of poly(arylene ether ketone)s is similar to that of polysulfone, involving aromatic dihalides and aromatic diphenolates. Since carbonyl is a weaker electron-withdrawing group titan sulfonyl, in most cases, difluorides need to be used to afford high-molecular-weight polymers. Typically potassium carbonate is used as a base to avoid the... 

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